Simultaneous interpenetrating polymer networks (sIPNs) from concurrent copper(I)-catalyzed azide alkyne cycloaddition "click chemistry" and atom transfer radical polymerization (ATRP) are described. Semi-sIPN of poly(ethylene glycol)/poly(2-hydroxyethyl methacrylate) (semi-PEG/PHEMA-sIPN) was first prepared via simultaneous "click chemistry" and ATRP from a mixture of poly(ethylene glycol)-diazide (N-3-PEG-N-3, M-n = 4000 g/mol), tetrakis(2-propynyloxymethyl)methane (TPOM), ethyl-2-bromobutyrate (EBB), CuBr, pentamethyldiethylenetriamine (PMDETA), and 2-hydroxyethyl methacrylate (HEMA) in dimethylformamide (DMF). Full sIPN of PEG/PHEMA (full-PEG/PHEMA-sIPN) was then prepared via simultaneous "click chemistry" and ATRP from a mixture of N-3-PEG-N-3 (M-n = 4000 g/mol), TPOM, EBB, CuBr, PMDETA, HEMA, and poly(ethylene glycol) diacrylate) (PEGDA, M-n = 575) in DMF. Both the semi- and full-sIPNs exhibit a fast gelation rate and high gel yield. The sIPNs also exhibit high swelling ratios and good mechanical and antifouling properties. The morphology and thermal behavior of the sIPNs were studied by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). These sIPNs could find applications as biomaterials for contact lenses, biomedical materials, artificial organs, and drug deliver), systems.